JP6033399B2 - Anticorrosion paint composition, anticorrosion coating film, and method for anticorrosion of substrate - Google Patents

Description

  The present invention relates to an anticorrosion coating composition, an anticorrosion coating film, and a method for preventing corrosion of a substrate, and more particularly, an anticorrosion coating composition capable of forming an anticorrosion coating film having excellent adhesion and corrosion resistance to a metal substrate. The present invention relates to a product, an anticorrosion coating film formed from the composition, and a metal substrate anticorrosion method using the composition.

  In order to prevent corrosion, large-scale steel structures such as ships, land structures and bridges are usually subjected to anticorrosion coating using an anticorrosion coating composition. In the anticorrosion coating, by applying an anticorrosion coating composition so as to form an anticorrosion coating having a thickness of several hundred to several thousand μm on the surface of the steel plate or the like, and shielding the surface of the steel plate or the like with the anticorrosion coating, Corrosion of the steel sheet or the like is prevented by preventing contact between the steel sheet or the like and oxygen, salt, water vapor or the like.

  As the anticorrosion paint composition, an epoxy anticorrosion paint composition is used. When forming a thick film with a thickness of several hundred to several thousand μm using such an epoxy anticorrosive coating composition, an amide wax type rocking agent is used as a sagging inhibitor / antisettling agent (thixotropic agent). Anticorrosive coating compositions containing modifiers have been used. The anticorrosion coating film obtained from this composition is excellent in adhesion to the surface of a substrate such as a steel structure and anticorrosion property under normal construction conditions.

  Specifically, the epoxy anticorrosive coating composition includes a coating composition containing a fatty acid amide wax-based thixotropic agent (Patent Document 1), and the thixotropic agent includes fatty acid amide wax, oxidized polyethylene wax, and organic bentonite. The coating composition used together (Patent Documents 2 and 3) is disclosed. Further, an epoxy anticorrosive coating composition using only oxidized polyethylene wax without using fatty acid amide wax as a thixotropic agent is also disclosed (Patent Document 4).

JP 2000-129168 A JP-A 63-275890 JP-A-63-183966 JP-A-4-91175

  Since structures such as ballast tanks of ships are also required to have anticorrosion properties, anticorrosion coating is performed. For such a structure, an epoxy anticorrosive coating composition is usually used, and in order to form an anticorrosive coating film having a sufficient film thickness, the coating composition containing an amide wax thixotropic agent is applied, After drying, the coating composition is further applied thereon and dried to form an anticorrosion coating (twice coating). At this time, not only the adhesion between the substrate and the coating film (or anticorrosion coating film) formed in the first time, but also the coating film (or anticorrosion coating film) formed in the first time, for corrosion prevention, The adhesion between the coating film (or anticorrosion coating film) formed in the second time is important.

  When coating an anticorrosion coating composition on such a ship structure, spray coating is often performed. In this case, for example, when spraying a wall surface or a ceiling surface, the spray dust tends to adhere to a surface different from the surface currently coated, for example, the floor surface.

  In particular, when the anticorrosion coating composition is applied by the two-time coating, the first coating film is formed on a part (A), and the coating film is not dried or dried while other The first coating may be formed on part (B), but when forming the coating on part (B), spray dust (or dry) on the coating formed on part (A) The composition which becomes spray dust may adhere. In such a case, since the spray dust is partially taken into the surface of the coating film until the coating film formed on the part (A) is dried, the second coating is applied to the part (A). When doing so, the spray dust adhering to the coating surface cannot be easily removed.

  The inventors of the present invention have used the conventional anti-corrosion coating composition such as the coating composition described in the above-mentioned patent document, and while performing spray coating, the spray dust as described above is generated, and the spray dust is generated. However, it turned out that it exists in the tendency to reduce the adhesiveness of the film | membrane formed on it.

  Also, when spraying the inside of a ship that is difficult to ventilate after painting such as a ballast tank, the composition that becomes spray dust may adhere to the floor surface of the ballast tank. Here, because of the structure of the ballast tank, the vapor of the solvent contained in the coating composition tends to stay in the vicinity of the floor surface. Therefore, the composition adhering to the floor surface or the like tends to be dried in a solvent atmosphere. It has been found that the spray dust generated in this case tends to significantly reduce the adhesion of the film formed thereon.

  Furthermore, the composition described in Patent Document 4 cannot be applied to a part that is required to form a thick film having a dry film thickness of 100 μm or more. It was necessary to change the composition of things.

  This invention is made | formed in view of such a condition, The subject of this invention is the anticorrosion coating composition for forming the anticorrosion coating film of 100 micrometers or more of dry film thickness, Comprising: An anti-corrosion coating composition with excellent anti-corrosion properties, and even if it adheres as spray dust to an object to be coated, it is difficult to reduce the adhesion of the film formed on the object to be coated (coating object). It is to provide a coating composition.

  As a result of intensive studies on the method for solving the above problems, the present inventors have found that an anticorrosion containing an epoxy resin, a curing agent, a silane coupling agent, an oxidized polyethylene wax and an extender pigment, and substantially free of fatty acid amide wax. The present inventors have found that the above-mentioned problems can be solved by the coating composition, and have completed the present invention. The configuration of the present invention is as follows.

  [1] A dry film containing an epoxy resin (A), a curing agent (B), a silane coupling agent (C), an oxidized polyethylene wax (D) and an extender pigment (E) and substantially free of fatty acid amide wax An anticorrosion coating composition for forming an anticorrosion coating film having a thickness of 100 μm or more.

  [2] The anticorrosion coating composition according to [1], which is used under conditions where spray dust of the anticorrosion coating composition adheres.

  [3] The oxide polyethylene wax (D) is contained in an amount of 0.01 to 3% by weight (nonvolatile content) with respect to 100% by weight of the nonvolatile content of the anticorrosion coating composition, according to [1] or [2] Anticorrosion paint composition.

[4] The anticorrosion coating composition according to any one of [1] to [3], further comprising bentonite and finely divided silica.
[5] The anticorrosion coating composition according to [4], wherein the fine silica is hydrophobic fine silica.

[6] The anticorrosive coating composition according to any one of [1] to [5], wherein the silane coupling agent (C) is an epoxy group-containing alkoxysilane compound.
[7] In any one of [1] to [6], the silane coupling agent (C) is included in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition. The anticorrosion coating composition as described.

  [8] The extender pigment (E) includes at least one pigment selected from the group consisting of silica, barium sulfate, calcium carbonate, talc, barite powder, dolomite and feldspar, and a flat pigment (F). The anticorrosion coating composition according to any one of [1] to [7].

  [9] The anticorrosion coating composition according to any one of [1] to [8], which is for spray coating.

[10] An anticorrosion coating film formed from the anticorrosion coating composition according to any one of [1] to [9].
[11] A substrate anticorrosion method comprising a step of applying the anticorrosion coating composition according to any one of [1] to [9] on a substrate.

According to the present invention, an anti-corrosion coating composition having excellent adhesion and anti-corrosion properties to a substrate, and even if it adheres as spray dust to an object to be coated, Thus, it is possible to obtain an anticorrosive coating composition that hardly lowers the adhesion of the coating.
In addition, the anticorrosion coating composition of the present invention is excellent in adhesion to a substrate even when a thick film having a dry film thickness of 100 μm or more is formed. It can be formed easily. In particular, an anticorrosive coating film having a sufficient film thickness can be easily formed by airless spraying or the like on a portion where a thick anticorrosion coating film such as a ballast tank needs to be formed.

FIG. 1 is a schematic view for explaining an adhesion test in Examples.

≪Anti-corrosion paint composition≫
The anticorrosive coating composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”) comprises an epoxy resin (A), a curing agent (B), a silane coupling agent (C), and an oxidized polyethylene wax (D). And an anticorrosive coating composition for forming an anticorrosive coating film having a dry film thickness of 100 μm or more, which contains an extender pigment (E) and does not substantially contain a fatty acid amide wax.
Since the composition of the present invention contains these (A) to (E) and does not substantially contain a fatty acid amide wax, it is an anticorrosive coating composition having excellent adhesion and anticorrosive properties to a substrate, Even if it adheres as spray dust to the object to be coated, it is a composition that hardly reduces the adhesion of the film formed thereon to the object to be coated. In addition, when spray coating is applied to narrow parts such as ballast tanks, there may be places where spray patterns overlap, and an anticorrosion coating film about three times the target film thickness may be formed. When forming a thick film (thick film having a dry film thickness of 300 μm or more), sagging of the composition is less likely to occur during coating, and the thick film can be easily formed.
For this reason, the composition of the present invention is an anticorrosive paint used for forming thick films of about 100 μm or more, for ship structures such as ballast tanks, for spray coating, and for the conditions where the spray dust of the composition of the present invention adheres. It is suitably used as a composition.

The conditions under which the spray dust of the composition of the present invention adheres are not particularly limited as long as the following spray dust is formed from the composition of the present invention.
Specifically, as such a condition, when the coating composition is spray-coated, a condition in which the coating composition adheres to a location different from the location where the coating is currently applied (the location where the coating is desired), more specifically, When spray coating large steel structures such as ships, land structures, bridges, etc., there must be a condition that there is a place to be painted on the floor surface 1 m or more below the spray coating location, Examples of the coating environment include conditions where the temperature of 10 to 40 ° C. and the humidity of 85% or less easily evaporates the solvent that can be contained in the composition.

“Spray dust” in the present invention refers to a location different from the location where the coating composition is currently applied (location to be applied), for example, a floor surface when a wall surface or a ceiling surface is applied. The coating composition adhering to is dried. Such spray dust usually adheres to a part away from a currently applied part (a part to be applied) to some extent when spray coating the coating composition.
Also, spray dust that causes a decrease in the adhesion of the film to the object to be coated tends to occur when an anticorrosive coating composition that requires the formation of a thick film is used. This is because the anticorrosion coating composition that requires the formation of a thick film does not sag when the thick film is formed, that is, the composition has excellent adhesion to the substrate. However, it is considered that the fatty acid amide wax is blended as a sagging inhibitor / antisettling agent (thixotropic agent) in response to this requirement.

In the present invention, the “coating film” refers to a film that has not been dried or completely dried after the anticorrosion coating composition is applied, and the “anticorrosion coating film” refers to a coating of the anticorrosion coating composition. Then, it means a film after drying and curing, and the “film” means a film (including dried and undried) formed from a coating composition (including an anticorrosive coating composition). .
In the present invention, “twice coating” refers to coating the composition of the present invention to form a coating film, followed by drying and curing as necessary, and further coating the same composition thereon. “Top coating” refers to coating on the anticorrosive coating film of the present invention a composition different from that formed the coating film.

  The composition of the present invention is preferably a two-component composition prepared by mixing a main ingredient component and a curing agent component from the viewpoint of storage stability and the like.

<Epoxy resin (A)>
The epoxy resin (A) is not particularly limited, and examples thereof include non-tar epoxy resins described in JP-A-11-343454 and JP-A-10-259351.

Examples of the epoxy resin (A) include polymers or oligomers containing two or more epoxy groups in the molecule, and polymers or oligomers generated by a ring-opening reaction of the epoxy groups. Examples of such epoxy resins include bisphenol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol type epoxy resins, dimer acid-modified epoxy resins, aliphatic epoxy resins, and alicyclic groups. An epoxy resin, an epoxidized oil type epoxy resin, etc. are mentioned.
Among these, bisphenol-type epoxy resins are preferable, bisphenol A-type and bisphenol F-type epoxy resins are more preferable, and bisphenol-type epoxy resins are more preferable from the viewpoint that an anticorrosion coating having excellent adhesion to a substrate can be formed. A type epoxy resin is particularly preferred.

  Examples of the epoxy resin (A) include epichlorohydrin-bisphenol A epoxy resin (bisphenol A diglycidyl ether type); epichlorohydrin-bisphenol AD epoxy resin; epichlorohydrin and bisphenol F (4,4 "-methylenebisphenol). Obtained bisphenol F type epoxy resin; epoxy novolak resin; alicyclic epoxy resin obtained from 3,4-epoxyphenoxy-3 ", 4" -epoxyphenylcarboxymethane, etc .; epichlorohydrin-bisphenol A Brominated epoxy resin in which at least one of the bonded hydrogen atoms is substituted with a bromine atom; Aliphatic epoxy resin obtained from epichlorohydrin and aliphatic dihydric alcohol; Polyfunctional epoxy resins obtained from phosphorus and tri (hydroxyphenyl) methane and the like.

  Examples of bisphenol A type epoxy resins that are particularly preferably used include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol A propylene oxide diester. Examples thereof include polycondensation products such as bisphenol A type diglycidyl ether such as glycidyl ether.

The epoxy resin (A) may be synthesized by a conventionally known method or may be a commercially available product.
As a commercially available product, “E028” (manufactured by Akira Ohtake Shin Chemical Co., Ltd., bisphenol A diglycidyl ether resin, epoxy equivalent of 180 to 190, viscosity of 12,000 to 15,000 mPa · s / 25 as a liquid at room temperature. ° C), “jER-807” (Mitsubishi Chemical Corporation, bisphenol F diglycidyl ether resin, epoxy equivalent 160-175, viscosity 3000-4500 mPa · s / 25 ° C.), “Flep 60” (Toray Fine Chemical Co., Ltd.) ), Epoxy equivalent of about 280, viscosity of about 17,000 mPa · s / 25 ° C., “E-028-90X” (manufactured by Akira Ohtake Shin Chemical Co., Ltd., xylene solution of bisphenol A diglycidyl ether resin (828 type epoxy) Resin solution), epoxy equivalent of about 210), etc.
As a semi-solid at room temperature, “jER-834” (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 230-270), “E-834-85X” (Otake Akira Shin Chemical Co., Ltd.) Manufactured, xylene solution of bisphenol A type epoxy resin (834 type epoxy resin solution), epoxy equivalent of about 300), etc.
“JER1001” (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 450-500), “E-001-75” (Otake Akira Shin Chemical Co., Ltd., bisphenol) A xylene solution of type A epoxy resin (1001 type epoxy resin solution), epoxy equivalent of about 630) and the like.

  The said epoxy resin (A) can be used individually by 1 type or in combination of 2 or more types.

  The epoxy resin (A) is preferably liquid or semi-solid at normal temperature (temperature of 15 to 25 ° C., the same shall apply hereinafter) from the viewpoint of obtaining a composition having excellent adhesion to the substrate.

  The epoxy equivalent of the epoxy resin (A) is preferably 150 to 1000, more preferably 150 to 600, and particularly preferably 180 to 500 from the viewpoint of corrosion resistance and the like.

  The weight average molecular weight measured by GPC (gel permeation chromatograph) of the epoxy resin (A) is not generally determined depending on the coating curing conditions (eg, normal dry coating or baking coating) of the resulting composition. However, the molecular weight is preferably 350 to 20,000.

The epoxy resin (A) is preferably contained in the composition of the present invention in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight.
When the composition of the present invention is a two-component composition comprising a main component and a curing agent component, the epoxy resin (A) is included in the main component, and the main component It is desirable that the component is contained in an amount of preferably 5 to 80% by weight, more preferably 5 to 50% by weight.

<Curing agent (B)>
The curing agent (B) is not particularly limited, and examples thereof include amine curing agents and acid anhydride curing agents, but amine curing such as aliphatic, alicyclic, aromatic, and heterocyclic systems. Agents are preferred.

  Examples of the aliphatic amine curing agent include alkylene polyamines and polyalkylene polyamines.

Examples of the alkylene polyamine include, for example, the formula: H ₂ N—R ¹ —NH ₂ (R ¹ is a divalent hydrocarbon group having 1 to 12 carbon atoms, and any hydrogen atom of the hydrocarbon group is carbon And optionally substituted with a hydrocarbon group of 1 to 10), specifically, methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trimethylhexa And methylene diamine.

Examples of the polyalkylene polyamine include the formula: H ₂ N— (C _m H _2m NH) _n H (m is an integer of 1 to 10, n is 2 to 10, and preferably an integer of 2 to 6 In particular, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine Etc.

  Other aliphatic amine curing agents include tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2 "-aminoethylamino) propane, triethylene-bis ( Examples include trimethylene) hexamine, bis (3-aminoethyl) amine, bis (hexamethylene) triamine, and bis (cyanoethyl) diethylenetriamine.

  Specific examples of the alicyclic amine curing agent include 1,4-cyclohexanediamine, 4,4 "-methylenebiscyclohexylamine, 4,4" -isopropylidenebiscyclohexylamine, norbornanediamine, and bis (aminomethyl). ) Cyclohexane, diaminodicyclohexylmethane, isophoronediamine, mensendiamine (MDA) and the like.

  Examples of the aromatic amine curing agent include bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, and aromatic polyamine compounds having two or more primary amino groups bonded to the benzene ring.

  More specifically, as this aromatic amine curing agent, for example, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethyl Phenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4 "-diaminodiphenyl ether, 4,4" -diaminobenzophenone, 4,4 "-diaminodiphenyl ether, 4,4" -diaminodiphenyl sulfone, 2, , 2 "-dimethyl-4,4" -diaminodiphenylmethane, 2,4 "-diaminobiphenyl, 2,3" -dimethyl-4,4 "-diaminobiphenyl, 3,3" -dimethoxy-4,4 "-diamino Biphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene And the like.

  Specific examples of the heterocyclic amine curing agent include N-methylpiperazine, morpholine, 1,4-bis- (3-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- ( 2 "-aminoethylpiperazine), 1- [2"-(2 "-aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane and the like.

  In addition, as the amine curing agent, for example, amines (amine compounds) described in JP-B-49-48480 can be used.

Other examples of the amine curing agent include diethylaminopropylamine and polyetherdiamine.
Examples of the amine curing agent include a modified product of the above-described amine curing agent, such as polyamide, polyamide amine (polyamide resin), amine adduct with an epoxy compound, Mannich compound (eg, Mannich modified polyamide amine), and Michael adduct. , Ketimine, aldimine, phenalkamine and the like.

The curing agent (B) may be obtained by synthesis by a conventionally known method or may be a commercially available product.
Commercially available products include, for example, “ACI Hardener K-39” (produced by PTI Japan), which is an aliphatic polyamine, “PA-66”, “PA-23” and “PA-290 (A ”” (Both manufactured by Akira Otake Shin Chemical Co., Ltd.), “MAD-204 (A)” (manufactured by Akira Otake Shin Chemical Co., Ltd.), a modified polyamine, and “Adeka Hardener EH-”, a Mannich modified polyamidoamine. 342W3 "(manufactured by ADEKA Co., Ltd.)," Sanmide CX-1154 "(manufactured by Sanwa Chemical Co., Ltd.), which is a Mannich-modified aliphatic polyamine, and" Cardlight NC556X80 "(manufactured by Cardlight) which is a phenorcamine adduct. Is mentioned.

  Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6- Examples include endomethylenetetrahydrophthalic anhydride.

  The said hardening | curing agent (B) can be used individually by 1 type or in combination of 2 or more types.

  The active hydrogen equivalent of the amine curing agent is preferably 50 to 1000, more preferably 80 to 400, from the viewpoint of corrosion resistance and the like.

  In the composition of the present invention, the curing agent (B) and the epoxy resin (A) have an equivalent ratio (amount of curing agent used / active hydrogen equivalent) / (amount of epoxy resin used / epoxy equivalent), The amount is preferably 0.3 to 1.5, more preferably 0.5 to 1.0.

  When the composition of the present invention is a two-component composition comprising a main component and a curing agent component, the curing agent (B) is included in the curing agent component. The curing agent component is preferably prepared so that the non-volatile content (solid content) is 50 to 100%, and the viscosity measured with an E-type viscometer at that time is easy to handle and coat. From the point of being excellent, etc., it is preferably 100,000 mPa · s / 25 ° C. or less, more preferably 50 to 10,000 mPa · s / 25 ° C.

<Silane coupling agent (C)>
By using the silane coupling agent (C), not only can the adhesion of the resulting anticorrosive coating to the substrate be improved, but also the anticorrosion properties such as salt water resistance of the resulting anticorrosive coating are improved. Therefore, the composition of the present invention preferably contains a silane coupling agent (C).
Such a silane coupling agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

The silane coupling agent (C) is not particularly limited, and a conventionally known silane coupling agent (C) can be used. The silane coupling agent (C) has at least two functional groups in the same molecule and has improved adhesion to the substrate. It is preferable that the compound can contribute to a decrease in the viscosity of the compound, and the formula: X-Si (OR) ₃ [X is a functional group capable of reacting with an organic substance (eg, amino group, vinyl group, epoxy group, mercapto Group, a halo group, or a hydrocarbon group containing these groups, etc. In addition, an ether bond or the like may be present in this hydrocarbon group) or an alkyl group, and OR is a hydrolyzable group (Example: methoxy group, ethoxy group) It is more preferable that it is a compound represented by this.

  Among these, the X group is an epoxy group, and the epoxy group-containing alkoxysilane compound can not only further improve the adhesion of the resulting anticorrosion coating to the substrate, but also the salt resistance of the resulting anticorrosion coating. The anticorrosion properties such as aqueous properties can be improved, the viscosity of the composition of the present invention can be lowered, and the coating workability is improved, which is preferable.

  As preferable silane coupling agents, specifically, “KBM403” (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), “Syra Ace S-510” (manufactured by JNC Corporation), etc. Is mentioned.

  In the composition of the present invention, the amount of the silane coupling agent (C) is preferably 0.01 to 10 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition. It is 05-10 weight part, More preferably, it is 0.3-5 weight part. When the composition containing the silane coupling agent (C) in such an amount is used, the performance of the anticorrosion coating such as adhesion to the substrate and anticorrosion is improved, and the viscosity of the composition of the present invention is lowered. As a result, painting workability is improved.

<Oxidized polyethylene wax (D)>
Since the composition of the present invention contains oxidized polyethylene wax (D), it has excellent adhesion to a substrate even when a thick film having a dry film thickness of 100 μm or more is formed, and sagging of the composition occurs during coating. It is difficult to form a thick film that can be easily formed. In particular, since the composition of the present invention contains the oxidized polyethylene wax (D) and the (A) to (C) and (E), such an effect is more exhibited.

Examples of the oxidized polyethylene wax (D) include resins obtained by oxidizing polyethylene and introducing polar groups.
Such oxidized polyethylene wax (D) may be synthesized by a conventionally known method or may be a commercially available product.
Examples of commercially available products include “Disparon 4200-20” manufactured by Enomoto Kasei Co., Ltd., “ASA D-120” manufactured by Ito Seiyaku Co., Ltd., and the like.

  The oxidized polyethylene wax (D) can be used alone or in combination of two or more.

  The average molecular weight measured by the solution viscosity measurement method of the oxidized polyethylene wax (D) is preferably 1000 to 5000, more preferably 2000 to 3500. When the average molecular weight is in the above range, a composition having excellent sagging-preventing properties and coating workability can be obtained.

  The acid value of the oxidized polyethylene wax (D) is preferably in the range of 10 to 40 KOHmg / g. It exists in the tendency for the anticorrosion coating film which is excellent in coating-film physical property to be obtained because an acid value exists in the said range.

The content (nonvolatile content) of the oxidized polyethylene wax (D) in the composition of the present invention is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the nonvolatile content in the composition of the present invention. More preferably, it is 0.2-2.0 weight part, More preferably, it is 0.5-1.8 weight part.
The composition of the present invention contains the above (A) to (C) and (E), and further contains the oxidized polyethylene wax (D) in the above amount, so that the composition can be dried without substantially containing the fatty acid amide wax. When a thick film having a film thickness of 100 μm or more is formed, the composition is excellent in adhesion to a substrate, and the composition can easily form a thick film in which sagging of the composition does not easily occur during coating.

<External pigment (E)>
The composition of the present invention includes the extender pigment (E), thereby forming an anticorrosion coating film having excellent corrosion resistance, salt water resistance, high temperature moisture resistance, and the like as well as cost advantages of the obtained composition. Can do.
The extender pigment (E) may be used alone or in combination of two or more.

Specific examples of the extender pigment (E) include silica, barium sulfate, calcium carbonate, dolomite, feldspar, barite powder, talc, and flat pigment (F).
Among these, the composition of the present invention is capable of forming an anticorrosion coating excellent in anticorrosion properties, salt water resistance, high temperature moisture resistance, and the like, and is therefore silica, barium sulfate, calcium carbonate, talc, dolomite, and feldspar. It is preferable to include at least one pigment selected from the group consisting of: and a flat pigment (F).
The said flat pigment (F) may be used individually by 1 type, and may be used in combination of 2 or more type.

As the flat pigment (F), a pigment having an average flake diameter of 30 to 200 μm and an average aspect ratio of 30 to 100 as measured with a particle size distribution analyzer is obtained. It is preferable from the viewpoints of improvement of creep, reduction of creep properties, relaxation of internal stress and the like.
Examples of the flat pigment (F) include mica, glass flakes and the like, and mica is preferable from the viewpoints of being able to form an anticorrosive coating film that is inexpensive, excellent in availability, and more excellent in the above effects.

  As the mica, a high aspect ratio mica having an aspect ratio of 30 to 90 is preferable from the viewpoint of improving the swelling resistance of the obtained anticorrosion coating film, reducing creep properties, relaxing internal stress, and the like. Specific mica includes “Suzolite Mica 200HK” (Kuraray Trading Co., Ltd., aspect ratio: 40 to 60).

In the composition of the present invention, the content of the extender pigment (E) is such that the anticorrosion coating having excellent anticorrosion properties and physical properties of the coating can be obtained, and the epoxy resin (A), the curing agent (B), and the silane. The amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight with respect to 100 parts by weight (nonvolatile content) of the coupling agent (C), oxidized polyethylene wax (D) and extender pigment (E). .
In addition, when the flat pigment (F) is blended in the composition of the present invention, the blending amount of the flat pigment (F) improves the performance of the anticorrosion coating film such as water corrosion resistance and flex resistance. In view of the above, the amount is preferably 1 to 40 parts by weight, more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the nonvolatile content of the composition of the present invention.

<Fatty acid amide wax>
The composition of the present invention is substantially free of fatty acid amide wax.
Examples of such fatty acid amide waxes include amide waxes synthesized from vegetable oil fatty acids and amines.

In applications where anticorrosion properties are required, particularly when an anticorrosion coating composition is used for a steel structure constituting a ship, the formed anticorrosion coating must have a film thickness of 100 μm or more, and an overlapping portion of spray patterns In consideration of the occurrence of this, sagging prevention is required to the extent that an anticorrosive coating film having a thickness of 300 μm or more can be formed. When the anticorrosion coating film having such a thickness is formed on a base material such as a wall surface or a ceiling surface, for example, the thickness of the anticorrosion coating is easy to sag during coating, excellent anticorrosion properties, and a uniform film thickness. It was not easy to obtain an anticorrosion coating film.
In particular, in a ballast tank, it is necessary to form an anticorrosive coating film with a thickness of 160 μm or more by one coating, and since it is a structure having a reinforcing material such as longi or transformer, an overlapping portion of spray patterns occurs. In consideration of the above, there are cases where sagging resistance capable of forming an anticorrosion coating film having a film thickness of 480 μm or more, which is three times the target film thickness, is required.

Therefore, the anticorrosive coating composition for forming the anticorrosive coating film having such a thickness does not sag during coating, that is, in order to obtain a composition having excellent adhesion to the substrate. Stoppers and anti-settling agents (thixotropic agents) have been used.
Various compounds are known as the anti-sagging agent and anti-settling agent (thixotropic agent), but fatty acid amide waxes have been used from the viewpoint of excellent anti-sagging effect. When forming a thick anticorrosion coating film, it was necessary to use a fatty acid amide wax.

However, as a result of intensive studies by the present inventors, the cause that the spray dust formed from the anticorrosive coating composition containing the conventional fatty acid amide wax reduces the adhesion of the film formed thereon to the object to be coated I found out.
Accordingly, when forming a thick anticorrosive coating, it is preferable to use a fatty acid amide wax, but the sprayed dust of the anticorrosive coating composition containing the fatty acid amide wax is coated on the film to be formed thereon. In view of reducing the adhesion to the composition, the composition of the present invention preferably contains no fatty acid amide wax.
Since the composition of the present invention contains the components (A) to (E), a thick anticorrosive coating film can be formed without substantially containing a fatty acid amide wax.

  Considering the above, it is preferable that the composition of the present invention does not substantially contain a fatty acid amide wax.

<Other ingredients>
In the composition of the present invention, in addition to the above (A) to (E), other anti-sagging / precipitating agent, solvent, plasticizer, curing accelerator, coloring pigment, inorganic dehydrating agent You may mix | blend (stabilizer), an antifoamer, an antifouling agent, etc. in the range which does not impair the objective of this invention.
These other components may be those conventionally known for use in anticorrosion coating compositions.

<Other anti-sagging and anti-settling agents>
The other anti-sagging / precipitating agent (compound other than oxidized polyethylene wax (D) and fatty acid amide wax) imparts thixotropy to the composition of the present invention, and adheres the composition to the substrate. Can be improved. The oxidized polyethylene wax (D) is also an anti-sagging / anti-settling agent, but the composition of the present invention may further contain other anti-sagging / anti-settling agents as required.
The other anti-sagging / precipitating agent is not particularly limited, and examples thereof include organic thixotropic agents and inorganic thixotropic agents.
The other anti-sagging / sedimentation agents may be used alone or in combination of two or more.

  Examples of the organic thixotropic agent include hydrogenated castor oil-based, vegetable oil polymerized oil-based, surfactant-based thixotropic agents, or thixotropic agents using two or more of these in combination.

Examples of the inorganic thixotropic agent include finely divided silica (usually, when measured by a scanning electron microscope observation method, the average particle diameter of primary particles is 40 nm or less, and the specific surface area is measured by the BET method. 50-410 m ² / g of silica), bentonite, silica treated with a silane compound, etc., bentonite (organic bentonite) treated with a quaternary ammonium salt, etc., ultrafine surface treated calcium carbonate, or , And mixtures thereof. Specifically, as an inorganic thixotropic agent, silica fine powder pulverized by a dry method [for example, product name: Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.], fine powder silica without surface treatment [for example, Japan Aerosil Co., Ltd., trade name: Aerosil 200], fine powder obtained by modifying silica fine powder with hexamethyldisilazane [for example, Nippon Aerosil Co., Ltd., trade name: Aerosil RX300], Silica fine powder is polydimethyl Fine powder modified with siloxane [for example, Nippon Aerosil Co., Ltd., trade name: Aerosil RY300], hydrophobic fine powder silica obtained by treating fine powder silica with dimethyldichlorosilane (Nippon Aerosil Co., Ltd., trade name: Aerosil R972) And organic bentonite (manufactured by Elementis Specialties, Inc., trade name: Benton SD-2).

Among these, as the other anti-sagging and anti-settling agent, fine silica (including those obtained by treating the surface with a silane compound or the like) from the viewpoint of obtaining a composition having excellent adhesion to the substrate. And bentonite (including those whose surfaces are treated with a quaternary ammonium salt or the like) are preferably used in combination.
In particular, it is more preferable to use hydrophobic fine powder silica obtained by treating fine powder silica with dimethyldichlorosilane in combination with organic bentonite. Specifically, when the oxidized polyethylene wax (D) is 1.2 parts by weight (nonvolatile content) or less in the coating composition, hydrophobic fine silica and organic bentonite are used in combination as an inorganic thixotropic agent. It is more preferable.

  When the other anti-sagging / anti-settling agent is blended with the composition of the present invention, the blending amount (non-volatile content) of the other anti-sagging / anti-settling agent from the viewpoint of coating workability, etc. Preferably it is 0.1-4 weight part with respect to 100 weight part of non volatile matters of this composition, More preferably, it is 0.1-2 weight part.

  The total content (nonvolatile content) of the oxidized polyethylene wax (D) and other anti-sagging and anti-settling agents in the composition of the present invention is excellent in balance in anti-sagging properties and coating workability. Is preferably 0.5 to 5 parts by weight, more preferably 0.7 to 3 parts by weight with respect to 100 parts by weight of the nonvolatile content of the composition of the present invention.

  At this time, the weight ratio (non-volatile content) of the content (nonvolatile content) of the oxidized polyethylene wax (D) and other anti-sagging / precipitating agent in the composition of the present invention Content (nonvolatile content): blended so that the content of the other anti-sagging / anti-settling agent (nonvolatile content) is preferably 15:85 to 85:15, more preferably 25:75 to 75:25 (However, the total non-volatile content of the oxidized polyethylene wax (D) and other anti-sagging and anti-settling agents is 100).

<solvent>
The solvent is not particularly limited, and a conventionally known solvent can be used. For example, xylene, toluene, methyl isobutyl ketone, methoxypropanol, methyl ethyl ketone, butyl acetate, butanol, isopropyl alcohol, propylene glycol monomethyl ether (PGM), etc. Is mentioned.
These solvents may be used alone or in combination of two or more.

When the solvent is blended in the composition of the present invention, the blending amount of the solvent is not particularly limited, and may be appropriately adjusted according to the coating method when the composition of the present invention is coated. Considering the paintability of the product, it is desirable that the non-volatile content of the composition of the present invention is preferably contained in an amount such that it is 55 to 98% by weight, more preferably 65 to 95% by weight.
In addition, when the composition of the present invention is spray-coated, the solvent preferably has a nonvolatile content of 55 to 95% by weight, more preferably 65 to 95% by weight, from the viewpoint of paintability and the like. It is desirable that it be contained in an amount such that it is 90% by weight.

<Plasticizer>
The composition of the present invention preferably contains a plasticizer from the viewpoint of improving the flexibility and weather resistance of the resulting anticorrosion coating film.
The said plasticizer may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the plasticizer, conventionally known ones can be widely used, and liquid hydrocarbon resins such as low boiling fractions obtained by thermally decomposing naphtha, petroleum resins solid at room temperature, xylene resins, coumarone indene resins, etc. Is mentioned. Specific examples include liquid hydrocarbon resins and flexibility-imparting resins described in JP-A-2006-342360.

  Among these, a liquid hydrocarbon resin, and a hydroxyl group-containing petroleum resin, a xylene resin, and a coumarone indene resin that are solid at room temperature are preferable from the viewpoint of good compatibility with the epoxy resin (A).

  Commercially available liquid hydrocarbon resins include “Nesiles EPX-L”, “Nesiles EPX-L2” (manufactured by NEVCIN / phenol-modified hydrocarbon resin), “HILENOL PL-1000S” (manufactured by KOLON Chemical / Liquid hydrocarbon resins), and commercial products of petroleum resins that are solid at room temperature include "Neopolymer E-100", "Neopolymer K-2", "Neopolymer K3" (above, Shin Nippon Petrochemical Co., Ltd.) (Manufactured by C9 type hydrocarbon resin) and coumarone indene resin are commercially available as "NOVARES CA 100" (manufactured by Rutgers Chemicals AG), and as xylene resin as "Nicanol Y-51" (Mitsubishi Gas Chemical ( Etc.).

  In the case where the plasticizer is blended in the composition of the present invention, the blending amount of the plasticizer is the composition 100 of the present invention from the viewpoint that an anticorrosive coating film having excellent weather resistance and crack resistance is obtained. Preferably it is 1-50 weight part with respect to a weight part, More preferably, it is 3-30 weight part.

<Curing accelerator>
It is preferable that the composition of the present invention contains a curing accelerator capable of contributing to adjustment of the curing speed, particularly acceleration.
Examples of the curing accelerator include tertiary amines.
The said hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specifically, for example, triethanolamine, dialkylaminoethanol, triethylenediamine [1,4-diazacyclo (2,2,2) octane], 2,4,6-tri (dimethylaminomethyl) phenol (example: commercial product) The name “Versamine EH30” (Henkel Hakusui Co., Ltd.) and the trade name “Ancamin K-54” (Air Products Japan Co., Ltd.)) may be mentioned.

  These curing accelerators are preferably blended in the composition of the present invention in an amount of 0.05 to 2.0% by weight.

<Coloring pigment>
Specific examples of the color pigment include titanium white, red rose, yellow red rose, and carbon black.
The said color pigment may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the color pigment is blended in the composition of the present invention, the blending amount of the color pigment is preferably 0.01 to 20 parts by weight, more preferably 100 parts by weight of the nonvolatile content of the composition of the present invention. Is 0.03 to 10 parts by weight.

  The extender pigment (E) and the color pigment are pigment volume concentrations in the anticorrosion coating film formed from the composition of the present invention (PVC, volume concentration of the extender pigment (E) and the color pigment in the anticorrosion coating film). Is preferably contained in the composition of the present invention in an amount of 10 to 75% by weight, preferably 20 to 45% by weight, from the viewpoint of anticorrosion and the like.

≪Anti-corrosion coating film≫
The anticorrosion coating film of the present invention is not particularly limited as long as it is formed from the composition of the present invention. However, a coating film is formed by applying the composition of the present invention on a substrate, and the coating composition is applied. It is preferable that the film is obtained by drying and curing the film.
Such anticorrosion coatings have excellent anticorrosion properties such as salt water resistance and high temperature and humidity resistance, and adhere to the substrate and adhere to the substrate even if they adhere as spray dust. It is excellent in the property that it is difficult to lower the properties.

  Although it does not restrict | limit especially as said base material, Since the effect of this invention can be exhibited more, etc., it is preferable that it is a base material by which corrosion resistance is calculated | required.

As such a base material, a base material made of steel, non-ferrous metal (zinc, aluminum, stainless steel, etc.) is preferable, and a ship, land structure, bridge or other structure made of these, more preferably a ship structure. is there. Among ship structures, a ballast tank is more preferable. The ballast tank may be provided with an anticorrosion by installing an anode such as zinc or zinc-aluminum. The current density during the anticorrosion is preferably 1 to 10 mA / m ² .

  As the substrate, in order to remove rust, fats and oils, moisture, dust, slime, salt, etc., and to improve the adhesion of the resulting anticorrosive coating film, the substrate surface is treated as necessary (for example, Blasting treatment (ISO8501-1 Sa2 1/2), power tool treatment, friction method, treatment to remove oil and dust by degreasing), from the viewpoint of anticorrosiveness of the base material, weldability, shearing property, If necessary, a coating material for forming a thin film such as a conventionally known primary anticorrosive coating material (shop primer) or other primer may be applied to the surface of the base material and dried.

The method of applying the composition of the present invention on the substrate is not particularly limited, and a conventionally known method can be used without limitation, but it is excellent in workability, productivity, etc., for a large area substrate. However, spray coating is preferable because it can be easily applied and the effects of the present invention can be further exerted.
Further, when the composition of the present invention is a two-component composition, the main component and the curing agent component may be mixed and sprayed or the like just before coating.

  The spray coating conditions may be adjusted as appropriate according to the thickness of the anticorrosion coating film to be formed. At the time of airless spraying, for example, primary (air) pressure: about 0.4 to 0.8 MPa, secondary (paint ) Pressure: Coating conditions may be set to about 10 to 26 MPa and gun moving speed of about 50 to 120 cm / second.

  The method for drying and curing the coating film is not particularly limited, and the coating film may be dried and cured by heating at about 5 to 60 ° C. in order to shorten the drying and curing time. The coating film is dried and cured by leaving it in the atmosphere for about 1 to 14 days.

The film thickness of the anticorrosion coating film may be 100 μm or more, and may be appropriately selected according to a desired application, but is preferably 100 to 450 μm, more preferably 250 to 400 μm.
When forming an anticorrosion coating film having such a film thickness, an anticorrosion coating film having a desired thickness may be formed by a single coating, or twice (if necessary) depending on the anticorrosion properties. An anticorrosive coating film having a desired thickness may be formed by painting. In view of being able to form an anticorrosion coating having excellent anticorrosion properties, it is preferable to form an anticorrosion coating having a thickness in the above-mentioned range by applying twice.

  When the anticorrosion coating film is formed on a ship structure such as a ballast tank as a base material, a thickness of about 300 μm is required. However, the composition of the present invention has adhesiveness to the base material, specifically, sagging prevention. Therefore, the anticorrosive coating film having such a thickness can be easily formed.

≪Base material anticorrosion method≫
The anticorrosion method for the substrate of the present invention is not particularly limited as long as it includes the step of applying the composition of the present invention on the substrate, but the coating film is formed by applying the composition of the present invention on the substrate. A method of preventing corrosion of the substrate by forming the coating film and drying and curing the coating film is preferable.
The substrate, coating method, etc. in this method may be the same as those described in the column for the anticorrosion coating film.

  In the anticorrosion method for the base material, a conventionally known top coat such as an antifouling paint may be applied on the obtained coating or anticorrosion coating, and dried and cured, depending on the desired application. Good.

For example, the anti-corrosion method for the ballast tank is performed as follows.
First, the composition of the present invention is spray-coated on the floor surface of the ballast tank (the first coating, a dry film thickness of about 160 μm), and the obtained coating film is dried or left to dry on the wall or ceiling. The surface is spray coated with the composition of the present invention. At this time, the composition that becomes spray dust adheres to the floor surface by drying, and drying proceeds in a solvent atmosphere. After the coating film on the floor surface is dried, the composition is sprayed again on the floor surface (second coating, dry film thickness of about 160 μm). Similarly, the wall and ceiling surfaces are again spray-coated with the above composition to form an anticorrosion coating having a thickness of about 320 μm on the floor, wall and ceiling.
The anti-corrosion method for such a ballast tank is, as described above, the object to be coated (here, the coating film obtained by the second coating and the dry coating film) formed thereon by spray dust. This is a condition in which the adhesiveness to the dry paint with spray dust obtained by the first coating is likely to be reduced, but such a decrease in adhesiveness is less likely to occur by using the composition of the present invention.
On the other hand, when the conventional anticorrosive coating composition is used, this decrease in adhesion is significant.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

The following tests (1) to (7) were performed on the anticorrosive coating films formed from the compositions obtained in the following Examples and Comparative Examples. The results are shown in Table 2.
In addition, in the following tests (1) to (5), in particular, when the obtained composition is used for a ship and further for a ballast tank, the result is required to be “◯”.

(1) Salt water resistance test The salt water resistance of the anticorrosion coating was measured according to JIS K-5600 6-1. Specifically, it was performed as follows.
Each of the compositions obtained in the following examples and comparative examples on a blasted steel plate (hereinafter also referred to as “test plate”) having dimensions of 150 mm × 70 mm × 1.6 mm (thickness) has a dry film thickness. The test plate with a coating film was spray-coated to a thickness of about 250 μm, and the obtained test plate with a coating film was dried in an atmosphere of 23 ° C. and 50% RH for 7 days to prepare a test plate with an anticorrosion coating film. Using this test plate with anticorrosion coating, the appearance of the anticorrosion coating after being immersed in 3% salt water at 40 ° C. for 90 days was visually evaluated according to the following criteria.
(Evaluation criteria)
○: No change in swelling, cracking, rust, peeling, or hue.
Δ: Slight defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue. X: Any of swelling, cracking, rust, peeling, and hue change is clearly recognized.

(2) Electrocorrosion resistance test A zinc anode was connected to a test plate with an anticorrosion coating film prepared in the same manner as the salt water resistance test so that the electric current density was 5 mA / m ² or less, and the test was conducted in 3% salt water at 40 ° C. The appearance of the anticorrosion coating after being immersed for 90 days was visually evaluated according to the following criteria.
(Evaluation criteria)
○: No change in swelling, cracking, rust, peeling, or hue.
Δ: Slight defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue. X: Any of swelling, cracking, rust, peeling, and hue change is clearly recognized.

(3) Salt spray test
In accordance with JIS K-5600 7-1, a test plate with an anticorrosion coating film prepared in the same manner as the salt water resistance test was continuously sprayed for 90 days under a condition of 35 ° C. with a salt water concentration of 5%. The appearance of the later anticorrosion coating film was visually evaluated according to the following criteria.
(Evaluation criteria)
○: No change in swelling, cracking, rust, peeling, or hue.
Δ: Slight defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue. X: Any of swelling, cracking, rust, peeling, and hue change is clearly recognized.

(4) High temperature and high humidity test The high temperature and high humidity resistance of the anticorrosion coating was measured according to JIS K-5600 7-2. Specifically, it was performed as follows.
Using a test plate with an anticorrosion coating prepared in the same manner as the salt water resistance test, the appearance of the anticorrosion coating after being held in a tester at a temperature of 50 ° C. and a humidity of 95% for 90 days was evaluated according to the following criteria.
(Evaluation criteria)
○: No change in swelling, cracking, rust, peeling, or hue.
Δ: Slight defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue. X: Any of swelling, cracking, rust, peeling, and hue change is clearly recognized.

(5) Double-coat adhesion The anti-corrosion coating film was coated twice in accordance with JIS K-5400 8.5.3. Specifically, it was performed as follows.
Each of the compositions obtained in the following examples and comparative examples was spray-coated on the test plate so as to have a dry film thickness of about 160 μm, thereby preparing a test plate with a coating film. The obtained test plate with a coating film was dried in an atmosphere of 23 ° C. and 50% RH for 1 day, and on the obtained test plate with a dry coating film, the same composition as the composition that formed the coating film was obtained. Spray coating was performed so that the dry film thickness was about 160 μm, and drying was performed in an atmosphere of 23 ° C. and 50% RH for 7 days to obtain a test plate with an anticorrosive coating film having a film thickness of 320 μm.

Using the obtained test plate with anticorrosion coating film, the peeling state (peeling rate) between the anticorrosion coating films was evaluated according to the following criteria. A description will be given along FIG.
An X-shaped cut 2 was made on one surface of the anticorrosion coating film of the obtained test plate with the anticorrosion coating film. At this time, the area in the square connecting the four ends of the two cuts of the cut 2 was defined as the cut-in area 3.
Then, a cellophane adhesive tape is applied on the X-shaped notch, and one end of the tape is peeled off at an angle close to 90 ° with respect to the surface of the anticorrosive coating, thereby evaluating the peeling state (peeling rate) between the anticorrosive coatings. did. The ratio of the anticorrosive coating film peeled off from the test plate with respect to the area 3 where the cut was made after the tape was peeled was roughly estimated by visual observation.
(Evaluation criteria)
○: No peeling at all Δ: 1 to 15% or less of the whole peeled off
X: The part which exceeds 15% of the whole has peeled.

(6) Adhesion on spray dust adhesion surface Adhesion on the spray dust (dust spray) adhesion surface was carried out in accordance with JIS K-5400 8.5.3. Specifically, the following (6-1) to (6-3) were performed.

(6-1)
In the following examples and comparative examples, a test plate having a size of 150 × 70 × 1.6 (thickness) mm is placed so that the surface thereof is substantially perpendicular to gravity, and the resulting anticorrosive coating film has a thickness of 160 μm. Each of the obtained anticorrosion coating compositions was applied to obtain a test plate with a coating film.
The same composition as the composition on which the coating film was formed was applied on the coating surface of the obtained test plate with a coating by spray coating from a height of about 3 m above the test plate. A composition that became spray dust by being dried was deposited on about 95% of the surface area. The test plate to which the composition that became the spray dust adhered was dried for one day in an atmosphere of 23 ° C. and 50% RH. On the obtained test plate with a dry coating film, the same composition as the composition on which the anticorrosion coating film was formed was again spray-coated so that the dry film thickness was about 160 μm, and the temperature was 23 ° C. and 50% RH. A test plate with an anticorrosion coating film having a thickness of about 320 μm was obtained by drying in an atmosphere for 7 days.
The conditions for adhering the composition that becomes the spray dust are conditions for reproducing conditions similar to an example of the condition for adhering the spray dust that may be generated when the composition of the present invention is used in an actual field. .

Then, cut the X-shaped cut into the anticorrosion coating surface of the obtained test plate with anticorrosion coating, affixed with cellophane adhesive tape on it, an angle close to 90 ° with one end of the tape relative to the anticorrosion coating surface The peeling state (peeling rate) between the anticorrosive coating films was evaluated according to the following criteria. In addition, the numerical value of the following evaluation criteria was estimated similarly to said (5).
(Evaluation criteria)
○: No peeling at all Δ: 1 to 15% or less of the whole peeled off
X: The part which exceeds 15% of the whole has peeled.

(6-2)
In the following examples and comparative examples, a test plate having a size of 150 × 70 × 1.6 (thickness) mm is placed so that the surface thereof is substantially perpendicular to gravity, and the resulting anticorrosive coating film has a thickness of 160 μm. Each of the obtained anticorrosion coating compositions was applied to obtain a test plate with a coating film.
On the coating film surface of the obtained test plate with a coating film, the same composition as the composition that formed the coating film was applied by spray coating from a height of about 1.5 m above the test plate. A composition that became spray dust by being dried was deposited on about 95% of the surface area of the film. Immediately after the composition was deposited, it was obtained in a 60 x 40 x 30 cm (height) cm plastic box with xylene sprayed on the bottom and at a height of 8 cm from the bottom of the box. The test plate to which the composition that became spray dust adhered was left to stand and dried for one day.
The conditions for adhering the composition to be the spray dust and the subsequent drying conditions reproduce conditions similar to an example of the conditions for adhering the spray dust that may be generated when the composition of the present invention is used in the actual site. It is a condition for.

  After drying in the above atmosphere for 1 day, the same composition as the composition that formed the coating film is again spray-coated on the obtained test plate with the dried coating film so that the dry film thickness is about 160 μm, By drying for 7 days in an atmosphere of 23 ° C. and 50% RH, a test plate with an anticorrosion coating film having a film thickness of about 320 μm was obtained.

Then, cut the X-shaped cut into the anticorrosion coating surface of the obtained test plate with anticorrosion coating, affixed with cellophane adhesive tape on it, an angle close to 90 ° with one end of the tape relative to the anticorrosion coating surface The peeling state (peeling rate) between the anticorrosive coating films was evaluated according to the following criteria. In addition, the numerical value of the following evaluation criteria was estimated similarly to said (5).
(Evaluation criteria)
○: No peeling at all Δ: 1 to 15% or less of the whole peeled off
X: The part which exceeds 15% of the whole has peeled.

(6-3)
(6-2) except that, in (6-2), the height from the test plate when the composition that becomes spray dust by being dried is adhered is changed from about 1.5 m to about 3.0 m. In the same manner as described above, the peeling state (peeling rate) between the anticorrosive coating films was evaluated according to the following criteria. In addition, the numerical value of the following evaluation criteria was estimated similarly to said (5).
(Evaluation criteria)
○: No peeling at all Δ: 1 to 15% or less of the whole peeled off
X: The part which exceeds 15% of the whole has peeled.

(7) Sagging stop property The viscosity of each of the anticorrosion coating compositions obtained in the following Examples and Comparative Examples was adjusted to 2000 mPa · s / 25 ° C. using xylene. The obtained anticorrosive coating composition was applied on a test plate installed so that the surface thereof was substantially parallel to gravity by using an airless coating machine so that the dry coating thickness was 300 μm, 400 μm or 500 μm. The state of the coating film (or anticorrosion coating film) that was allowed to stand for 1 day after coating was visually observed, and sagging resistance was evaluated according to the following criteria.
(Evaluation criteria)
○: Sagging is less than 5 mm with a dry coating film of 500 μm.
○ Δ: Sagging is 5 mm or more with a dry coating film of 500 μm, but sagging is less than 5 mm with a drying coating film of 400 μm.
Δ: Sagging is 5 mm or more when the dried coating film is 400 μm, but sagging is less than 5 mm when the dried coating film is 300 μm.
X: Sagging is 5 mm or more at a dry coating film of 300 μm.

  The materials used in the examples of the present invention are shown in Table 1 below.

[Example 1]
As shown in Table 2 below, in a container, 19 parts by weight of epoxy resin (Note 1), 10 parts by weight of petroleum resin (Note 3), 4 parts by weight of liquid petroleum resin (Note 5), 5.5 parts by weight of xylene, butanol 1 part by weight, 1 part by weight of PGM, 1 part by weight of silane coupling agent (Note 6), 23 parts by weight of talc (Note 7), 6 parts by weight of mica (Note 8), 15 parts by weight of potassium feldspar (Note 9), titanium Put 6 parts by weight of white (Note 10), 1.5 parts by weight of yellow petal (Note 11) and 7 parts by weight of oxidized polyethylene wax (Note 14), add glass beads to it, and use a paint shaker These compounding ingredients were mixed. Subsequently, the main ingredient component was prepared by removing the glass beads.

Further, as shown in Table 2 below, 9.4 parts by weight of polyamidoamine (Note 18), 4.7 parts by weight of modified polyamine (Note 19), 0.1 part by weight of tertiary amine (Note 20), and PGM 0 A hardener component was prepared by mixing 8 parts by weight using a high speed disper.
A composition was prepared by mixing the obtained main ingredient component and curing agent component before coating.

[Examples 2 to 10 and Comparative Examples 5 to 6]
A composition was prepared in the same manner as in Example 1 except that the components and amounts to be blended in the main component and the curing agent component were changed as shown in Table 2 below.

[Comparative Examples 1-4]
The ingredients and amounts to be blended in the main ingredient component and the curing agent ingredient are changed as shown in Table 2 below. Further, when the main ingredient component is prepared, the main ingredient component having the composition in Table 2 is painted in the same manner as in Example 1. After dispersing with a shaker, glass beads were removed, dispersed at 56-60 ° C. using a high speed disperser, and then cooled to 30 ° C. or lower to prepare a main ingredient component. The curing agent was prepared in the same manner as in Example 1.

1: Anticorrosion coating film 2: X-shaped cut 3: Area with cut

Claims (10)

Contains epoxy resin (A), curing agent (B), silane coupling agent (C), oxidized polyethylene wax (D) and extender pigment (E), substantially free of fatty acid amide wax, dry film thickness of 100 μm or more An anticorrosive coating composition for forming an anticorrosive coating film and for ships . Against nonvolatile content 100% by weight of the anticorrosive coating composition, the in an amount of 0.01 to 3% by weight of polyethylene wax (D) oxide (nonvolatile content), anticorrosive coating composition according to claim 1. Furthermore, the anticorrosion coating composition of Claim 1 or 2 containing a bentonite and fine powder silica. The anticorrosion coating composition according to claim 3 , wherein the finely divided silica is hydrophobic finely divided silica. The anticorrosion coating composition according to any one of claims 1 to 4 , wherein the silane coupling agent (C) is an epoxy group-containing alkoxysilane compound. The anticorrosion according to any one of claims 1 to 5 , comprising the silane coupling agent (C) in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition. Paint composition. The extender pigment (E) comprises at least one pigment selected from the group consisting of silica, barium sulfate, calcium carbonate, talc, barite powder, dolomite and feldspar, and a flat pigment (F). The anticorrosion coating composition according to any one of to 6 . The anticorrosion coating composition according to any one of claims 1 to 7 , which is used for spray coating. The anticorrosion coating film formed from the anticorrosion coating composition of any one of Claims 1-8 . The base material anticorrosion method including the process of apply | coating the anticorrosion coating composition of any one of Claims 1-8 on a base material.

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